EP0205124B1 - Process for the preparation of polyarylene polyethers containing phosphorous - Google Patents

Process for the preparation of polyarylene polyethers containing phosphorous Download PDF

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EP0205124B1
EP0205124B1 EP86107728A EP86107728A EP0205124B1 EP 0205124 B1 EP0205124 B1 EP 0205124B1 EP 86107728 A EP86107728 A EP 86107728A EP 86107728 A EP86107728 A EP 86107728A EP 0205124 B1 EP0205124 B1 EP 0205124B1
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phosphorus
polycondensation
polyarylene ethers
preparation
containing polyarylene
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EP0205124A1 (en
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Werner Dr. Ude
Joachim Dr. Knebel
Günter Dr. Schröder
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Roehm GmbH Darmstadt
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)

Definitions

  • the invention relates to a process for the preparation of phosphorus-containing polyarylene ethers, which are flame-resistant organic plastics with a very high decomposition temperature.
  • phosphorus-containing polyarylene ethers which differ from those of S. Hashimoto et al., Journal of Makromol. Sci. Chem., A 11 (12), pages 2167-2176 (1977) differentiate phosphorus-containing aromatic polyethers in that they have a higher reduced viscosity, ie a higher molecular weight, and are masses of considerable strength and typical plastic properties with good self-extinguishing properties.
  • Their reduced viscosity ⁇ sp / c is at least 0.25 dl / g.
  • phosphorus-containing polyarylene ethers are prepared by polycondensation of bifunctional aromatic compounds which carry fluorine atoms and hydroxyl groups as reactive groups and of which at least one compound has a partial phosphine or phosphine oxide structure. Response times of 2 to 10 hours are required for this.
  • a major disadvantage for the production of substances having such plastic properties is that the technically difficult to access and therefore expensive fluorine compounds are required as polycondensation partners for their formation.
  • the object is achieved in that by polycondensation of dichlorinated diphenyl or triphenylphosphine oxides of the formula 1 with bisphenols of the formula 11 in reaction times which are in the range from at least 12 to generally 100, preferably 16 to 80 hours, phosphorus-containing polyarylene ether with ⁇ sp / c ⁇ 0.25 dl / g can be obtained, which as such can be processed into masses with plastic properties.
  • the invention relates primarily to phosphorus-containing polyarylene ethers consisting of repeating units of the structure where X is one of the groups is, with a reduced viscosity ⁇ sp / c> 0.25 dl / g, phosphorus-containing polyarylene ether, consisting of recurring units of the structure and phosphorus-containing polyarylene ethers consisting of repeating units of the structure
  • diphenols such as 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis-bis (4-hydroxyphenyl) xanthene, 3, 8-dihydroxy-5a, 10b - diphenyl-coumarano-2 ', 3', 2,3-coumaran, 4,4-dihydroxyphenyladamantane and phenolphthalein.
  • diphenols such as 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis-bis (4-hydroxyphenyl) xanthene, 3, 8-dihydroxy-5a, 10b - diphenyl-coumarano-2 ', 3', 2,3-coumaran, 4,4-dihydroxyphenyladamantane and phenolphthalein.
  • n is a number corresponding to the degree of polycondensation of the polyarylene ether obtained or an average value of at least 10.
  • the end groups E can be unreacted chlorine atoms or hydrogen atoms of the phenolic hydroxyl groups. Hydroxyl end groups are used for stabilization the polymers advantageously etherified, for example with methyl chloride or other alkylating or arylating agents, or reacted with acylating agents to give corresponding esters.
  • the polycondensation conditions are particularly important with regard to the use of suitable solvents, e.g. Chlorobenzene or N-methylpyrrolidone, the details of DE-A 3 203 186 or US-A 4 492 805 or that of Hashimoto et al. analogue.
  • suitable solvents e.g. Chlorobenzene or N-methylpyrrolidone
  • the strongly basic condensing agents e.g. Chlorobenzene or N-methylpyrrolidone
  • the alkali compounds sodium or potassium carbonate are used in an amount equivalent to the amount of chlorine to be split off.
  • the alkali can be used in limited excess.
  • the dichloro derivatives of methyl-diphenylphosphine oxide and triphenylphosphine oxide are preferred.
  • the chlorine groups are preferably para to the carbon atom bonded to the phosphorus atom.
  • Preferred representatives of compound I are 4,4'-dichlorotriphenylphosphine oxide and 4,4'-dichlorodiphenylmethylphosphine oxide.
  • the aromatic bisphenols 11 carry their phenolic hydroxyl groups on separate phenylene nuclei. These are connected by R "as defined above.
  • the invention thus also includes those groups R "which are bridged several times with the phenyl groups bonded to the free valences.
  • a clear, yellow, flexible cast film (Mw according to GPC in DMF, polystyrene as calibration substance: 83 900) is obtained from chloroform.
  • Example 2 The procedure of Example 1 is applied to the reaction of 0.05 mole 4,4'-dichlorodiphenylmethylphosphine oxide. 16 g of a polyether with a specific viscosity of 0.50 dl / g, lin chloroform) are obtained.
  • Example 1 The procedure of Example 1 is applied to the reaction of 0.05 mole 4,4'-dichlorotriphenylphosphine oxide.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Fireproofing Substances (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von phosphorhaltigen Polyarylenäthern, die schwer brennbare organische Kunststoffe mit sehr hoher Zersetzungstemperatur darstellen.The invention relates to a process for the preparation of phosphorus-containing polyarylene ethers, which are flame-resistant organic plastics with a very high decomposition temperature.

Aus derDE-A 3 203 186 sind phosphorhaltige Polyarylenäther bekannt, die sich gegenüber den von S. Hashimoto et al., Journal of Makromol. Sci. Chem., A 11 (12), Seiten 2167-2176 (1977) beschriebenen phosphorhaltigen aromatischen Polyäthern dadurch unterscheiden, daß sie eine höhere reduzierte Vikosität, d.h. ein höheres Molekulargewicht haben und Massen von erheblicher Festigkeit und typischen Kunststoffeigenschaften mit guten Selbstlöscheigenschaften darstellen. Ihre reduzierte Viskosität ηsp/c liegt bei wenigstens 0,25 dl/g.From DE-A 3 203 186, phosphorus-containing polyarylene ethers are known which differ from those of S. Hashimoto et al., Journal of Makromol. Sci. Chem., A 11 (12), pages 2167-2176 (1977) differentiate phosphorus-containing aromatic polyethers in that they have a higher reduced viscosity, ie a higher molecular weight, and are masses of considerable strength and typical plastic properties with good self-extinguishing properties. Their reduced viscosity η sp / c is at least 0.25 dl / g.

Die Herstellung dieser phosphorhaltigen Polyarylenäther erfolgt durch Polykondensation von bifunktionellen aromatischen Verbindungen, die Fluoratome und Hydroxylgruppen als reaktive Gruppen tragen und von denen mindestens eine Verbindung eine Phosphin- bzw. Phosphinoxidteilstruktur aufweist. Dafür werden Reaktionszeiten von 2 bis 10 Stunden benötigt. Ein großer Nachteil für die Herstellung solche Kunststoffeigenschaften aufweisender Substanzen ist, daß zu deren Bildung die technisch schwer zugänglichen und damit teuren Fluorverbindungen als Polykondensationspartner benötigt werden.These phosphorus-containing polyarylene ethers are prepared by polycondensation of bifunctional aromatic compounds which carry fluorine atoms and hydroxyl groups as reactive groups and of which at least one compound has a partial phosphine or phosphine oxide structure. Response times of 2 to 10 hours are required for this. A major disadvantage for the production of substances having such plastic properties is that the technically difficult to access and therefore expensive fluorine compounds are required as polycondensation partners for their formation.

Die Verwendung von chlorhaltigen und damit besser verfügbaren und billigeren Ausgangsverbindungen zur Herstellung phosphörhaltiger Polyäther durch Polykondensation, von z.B. Bis(p-chlorphenyl)phenylphosphinoxid mit aromatischen Bisphenolen in Gegenwart von Alkali bei hohen Temperaturen in einem hochsiedenden polaren Lösungsmittel innerhalb von 10 Stunden ist aus der Arbeit von S. Hashimoto et al. bekannt. Die Polyäther hatten eine verhältnismäßig niedrige reduzierte Viskosität ηsp/c ≤ 0,15 dl/g. Sie bestanden zum Teil aus braunen, viskosen Ölen, waren zum Teil gummiartige Massen oder krümelige Pulver. Aus den festen Reaktionsprodukten konnten keine Massen mit Kunststoffeigenschaften erhalten werden.The use of chlorine-containing and therefore more readily available and cheaper starting compounds for the production of phosphorus-containing polyethers by polycondensation, for example bis (p-chlorophenyl) phenylphosphine oxide with aromatic bisphenols in the presence of alkali at high temperatures in a high-boiling polar solvent within 10 hours, is from work by S. Hashimoto et al. known. The polyethers had a relatively low reduced viscosity η sp / c ≤ 0.15 dl / g. They consisted partly of brown, viscous oils, partly rubber-like masses or crumbly powders. No masses with plastic properties could be obtained from the solid reaction products.

Es bestand daher die Aufgabe, phosphorhaltige Polyarylenäther, die sich in ihren Eigenschaften, d.h. besonders in einem höheren ηsp/c und mit Kunststoffeigenschaften, von den von Hashimoto et al. beschriebenen phosphorhaltigen Polyarylenäthern unterscheiden, und die ausgehend von dichlorierten aromatischen Phosphorverbindungen hergestellt werden, bereit zu stellen.It was therefore the task of phosphorus-containing polyarylene ethers which differ in their properties, ie especially in a higher η sp / c and with plastic properties, from those described by Hashimoto et al. distinguish described phosphorus-containing polyarylene ethers, and which are prepared starting from dichlorinated aromatic phosphorus compounds.

Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß durch Polykondensation von dichlorierten Diphenyl- bzw. Triphenylphosphinoxiden der Formel 1 mit Bisphenolen der Formel 11 in Reaktionszeiten, die im Bereich von mindestens 12 bis im allgemeinen 100, bevorzugt 16 bis 80 Stunden liegen, phosphorhaltige Polyarylenäther mit ηsp/c ≥ 0,25 dl/g erhalten werden, die sich als solche zu Massen mit Kunststoffeigenschaften verarbeiten lassen.According to the invention the object is achieved in that by polycondensation of dichlorinated diphenyl or triphenylphosphine oxides of the formula 1 with bisphenols of the formula 11 in reaction times which are in the range from at least 12 to generally 100, preferably 16 to 80 hours, phosphorus-containing polyarylene ether with η sp / c ≥ 0.25 dl / g can be obtained, which as such can be processed into masses with plastic properties.

Die Erfindung betrifftein Verfahren zur Herstellung von phosphorhaltigen Polyarylenäthern der Struktur

Figure imgb0001
mit einer reduzierten Viskosität ηsp/c > 0,25 dl/g durch Polykondensation eines Bis-(chlorphenyl)phos- phinoxids 1 mit einem Bisphenol 11 bei Temperaturen von 100-300 Grad C, in Gegenwart eines Lösungsmittels für den Polyarylenäther und in Gegenwart einer zur Halogenmenge äquivalenten Alkalimenge
Figure imgb0002
Figure imgb0003
wobei

  • R jeweils ein Wasserstoffatom oder R...R zusammengenommen eine kovalente Einfachbindung oder ein Sauerstoffstom, ein Schwefelatom, eine Sulfonyl-, Carbony-, Methylen-oder Isopropylidengruppe,
  • R' eine Alkyl- oder Arylgruppe,
  • R" eine Einfachbindung oder ein Sauerstoffatom oder ein Schwefelatom oder ein 5 bis 15 C-Atome enthaltender organischer Rest, dessen freie Valenzen von quartären C-Atomen ausgehen oder die oben genannte Formel 11 Phenolphthalein darstellt,
  • E eine Engdruppe, bestehend aus Chlor oder Wasserstoff bzw. Hydroxy- oder einer Alkyl- bzw. Alkoxy-, oder Aryl- bzw. Aryloxy- oder Acyl- bzw. Acyloxygruppe und
  • n ein Mittelwert von mindestens 10 ist, dadurch gekennzeichnet, daß die Polykondensation in Reaktionszeiten von mindestens 12 Stunden durchgeführt wird.
The invention relates to a process for the preparation of phosphorus-containing polyarylene ethers of the structure
Figure imgb0001
 with a reduced viscosity η sp / c> 0.25 dl / g by polycondensation of a bis- (chlorophenyl) phosphine oxide 1 with a bisphenol 11 at temperatures of 100-300 degrees C, in the presence of a solvent for the polyarylene ether and in the presence an amount of alkali equivalent to the amount of halogen
Figure imgb0002
Figure imgb0003
 in which
  • R each represents a hydrogen atom or R ... R taken together is a covalent single bond or an oxygen atom, a sulfur atom, a sulfonyl, carbonyl, methylene or isopropylidene group,
  • R 'is an alkyl or aryl group,
  • R "is a single bond or an oxygen atom or a sulfur atom or an organic radical containing 5 to 15 carbon atoms, the free valences of which originate from quaternary carbon atoms or the above-mentioned formula 11 represents phenolphthalein,
  • E is a narrow group consisting of chlorine or hydrogen or hydroxyl or an alkyl or alkoxy or aryl or aryloxy or acyl or acyloxy group and
  • n is an average of at least 10, characterized in that the polycondensation is carried out in reaction times of at least 12 hours.

Die Erfindung betrifft vor allem phosphorhaltige Polyarylenäther bestehend aus wiederkehrenden Einheiten der Struktur

Figure imgb0004
worin X eine der Gruppen
Figure imgb0005
ist, mit einer reduzierten Viskosität ηsp/c > 0,25 dl/g, phosphorhaltige Polyarylenäther, bestehend aus wiederkehrenden Einheiten der Struktur
Figure imgb0006
und phosphorhaltige Polyarylenäther bestehend aus wiederkehrenden Einheiten der Struktur
Figure imgb0007
 The invention relates primarily to phosphorus-containing polyarylene ethers consisting of repeating units of the structure
Figure imgb0004
 where X is one of the groups
Figure imgb0005
 is, with a reduced viscosity η sp / c> 0.25 dl / g, phosphorus-containing polyarylene ether, consisting of recurring units of the structure
Figure imgb0006
 and phosphorus-containing polyarylene ethers consisting of repeating units of the structure
Figure imgb0007

Die Polyarylenäther werden erfindungsgemäß in Polykondensationszeiten von≥12 Stunden durch Polykondensation von dichlorierten phosphorhaltigen Monomeren der Struktur I

Figure imgb0008
worin R = H oder R...R eine Einfachbindung oder O, S, S02, CO, CH2, C(CH3)2 und

  • R' eine Aryl-, insbesondere Phenyl- oder Alkyl-, insbesondere Methylgruppe ist mit Bisphenolen der Struktur II erhalten
    Figure imgb0009
     worin R" die oben angegebenen Bedeutungen hat. Beispiele für R" sind in der Struktur
    Figure imgb0010
    enthalten, worin Y = - CO - O, o - C6H4, - O - (0-C6H4) sein kann.
According to the invention, the polyarylene ethers are obtained in polycondensation times of ≥12 hours by polycondensation of dichlorinated phosphorus-containing monomers of structure I.
Figure imgb0008
 wherein R = H or R ... R is a single bond or O, S, S0 2 , CO, CH 2 , C (CH 3 ) 2 and
  • R 'an aryl, especially phenyl or alkyl, especially methyl group is obtained with bisphenols of structure II
    Figure imgb0009
     where R "has the meanings given above. Examples of R" are in the structure
    Figure imgb0010
     contain, where Y = - CO - O, o - C 6 H 4 , - O - ( 0 -C 6 H 4 ).

Dazu zählen Diphenole wie beispielsweise 4,4'-Dihydroxydiphenyl, 4,4'-Dihydroxydiphenyläther, 9,9-Bis-(4-hydroxyphenyl)fluoren, 9,9-Bis-Bis-(4--hydroxyphenyl)xanthen, 3,8-Dihydroxy-5a, 10b--diphenyl-cumarano-2',3',2,3-cumaran, 4,4-Dihydroxyphenyladamantan und Phenolphthalein.These include diphenols such as 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis-bis (4-hydroxyphenyl) xanthene, 3, 8-dihydroxy-5a, 10b - diphenyl-coumarano-2 ', 3', 2,3-coumaran, 4,4-dihydroxyphenyladamantane and phenolphthalein.

Die nach dem erfindungdsgemäßen Verfahren hergestellten Polykondensate mit einem ηsp/0≥25 dl/g haben danach die Struktur III

Figure imgb0011
The polycondensates produced by the process according to the invention with an η sp / 0≥25 dl / g then have the structure III
Figure imgb0011

Die Bedeutung von R, R' und R" ist oben erläutert, n ist eine dem Polykondensationsgrad des erhaltenen Polyarylenäthers entsprechende Zahl bzw. ein Mittelwert von mindestens 10. Die Endgruppen E können nicht umgesetzte Chloratome oder Wasserstoffatome der phenolischen Hydroxylgruppen sein. Hydroxylendgruppen werden zur Stabilisierung der Polymeren vorteilhaft veräthert, z.B. mit Methylchlorid oder anderen Alkylierungs- bzw. Arylierungsmitteln, oder mit Acylierungsmitteln zu entsprechenden Estern umgesetzt.The meaning of R, R 'and R "is explained above, n is a number corresponding to the degree of polycondensation of the polyarylene ether obtained or an average value of at least 10. The end groups E can be unreacted chlorine atoms or hydrogen atoms of the phenolic hydroxyl groups. Hydroxyl end groups are used for stabilization the polymers advantageously etherified, for example with methyl chloride or other alkylating or arylating agents, or reacted with acylating agents to give corresponding esters.

Es wurde gefunden, daß zur Herstellung phosphorhaltiger Polyarylenäther mit dem erforderlichen Mindestwert der reduzierten Viskosität und der Struktur III, durch Polykondensation eines dichlorierten Phosphinoxids der Struktur I mit einem Bisphenol der Struktur II bei Reaktionstemperaturen im Bereich von 100 bis 300°C in Gegenwart eines polaren Lösungsmittels, Polykondensationszeiten von mindestens 12 Stunden benötigt werden.It has been found that for the production of phosphorus-containing polyarylene ethers with the required minimum value of reduced viscosity and structure III, by polycondensation of a dichlorinated phosphine oxide of structure I with a bisphenol of structure II at reaction temperatures in the range from 100 to 300 ° C. in the presence of a polar solvent , Polycondensation times of at least 12 hours are required.

Die Polykondensationsbedingungen sind insbesondere hinsichtlich der Verwendung geeigneter Lösungsmittel, wie z.B. Chlorbenzol oder N-Methylpyrrolidon, den Angaben der DE-A 3 203 186 bzw. der US-A 4 492 805 oder derer von Hashimoto et al. analog. Das gleiche gilt auch für die starkbasischen Kondensationsmittel. Als solche werden insbesondere die Alkaliverbindungen Natrium- oder Kaliumcarbonat, in einer zur abzuspaltenden Chlormenge äquivalenten Menge eingesetzt.The polycondensation conditions are particularly important with regard to the use of suitable solvents, e.g. Chlorobenzene or N-methylpyrrolidone, the details of DE-A 3 203 186 or US-A 4 492 805 or that of Hashimoto et al. analogue. The same applies to the strongly basic condensing agents. As such, in particular the alkali compounds sodium or potassium carbonate are used in an amount equivalent to the amount of chlorine to be split off.

Um den notwendigen Polykondensationsgrad n zu erreichen, ist es erforderlich, daß die beiden Ausgangsverbindungen I und 11 möglichst genau mit ihren funktionellen Gruppen im stöchiometrischen Verhältnis 1:1 vorliegen.In order to achieve the necessary degree of polycondensation n, it is necessary that the two starting compounds I and 11 are present as precisely as possible with their functional groups in a stoichiometric ratio of 1: 1.

Das Alkali kann in begrenztem Überschuß eingesetzt werden.The alkali can be used in limited excess.

Unter den phosphorhaltigen Ausgangskomponenten der Struktur 1 sind die Dichlorderivate des Methyl-diphenylphosphinoxyds und des Triphenylphosphinoxids bevorzugt. Die Chlorgruppen stehen vorzugsweise in para-Stellung zu dem an das Phosphoratom gebundene C-Atom. Bevorzugte Vertreter der Verbindung I sind 4,4'-Dichlortriphenylphosphinoxid und 4,4'-Dichlordiphenylmethylphosphinoxid.Among the phosphorus-containing starting components of structure 1, the dichloro derivatives of methyl-diphenylphosphine oxide and triphenylphosphine oxide are preferred. The chlorine groups are preferably para to the carbon atom bonded to the phosphorus atom. Preferred representatives of compound I are 4,4'-dichlorotriphenylphosphine oxide and 4,4'-dichlorodiphenylmethylphosphine oxide.

Die aromatischen Bisphenole 11 tragen ihre phenolischen Hydroxylgruppen an getrennten Phenylenkernen. Diese sind durch R" wie oben definiert miteinander verbunden.The aromatic bisphenols 11 carry their phenolic hydroxyl groups on separate phenylene nuclei. These are connected by R "as defined above.

Beispiele der Bisphenole 11 sind die im folgenden wiedergegebenen Verbindungen (1) bis (8):

Figure imgb0012

  • 4,4'-Dihydroxydiphenyl (1)
    Figure imgb0013
  • 4,4'-Dihydroxydiphenyläther (2)
    Figure imgb0014
  • 4,4'-Dihydroxydiphenylsulfid (3)
    Figure imgb0015
  • 9,9'-Bis-(4-hydroxyphenyl)fluoren (4)
    Figure imgb0016
  • Phenolphthalein (5)
    Figure imgb0017
  • 9,9-Bis-(4-hydroxyphenyl)xanthen (6)
    Figure imgb0018
  • 4,4'-Dihydroxyphenyl-adamantan (7)
    Figure imgb0019
  • 3,8-Dihydroxy-5a, 10b-diphenyl-cumarano--2',3',2,3-cumaran. (8)
Examples of bisphenols 11 are the compounds (1) to (8) shown below:
Figure imgb0012
  • 4,4'-dihydroxydiphenyl (1)
    Figure imgb0013
  • 4,4'-dihydroxydiphenyl ether (2)
    Figure imgb0014
  • 4,4'-dihydroxydiphenyl sulfide (3)
    Figure imgb0015
  • 9,9'-bis (4-hydroxyphenyl) fluorene (4)
    Figure imgb0016
  • Phenolphthalein (5)
    Figure imgb0017
  • 9,9-bis (4-hydroxyphenyl) xanthene (6)
    Figure imgb0018
  • 4,4'-dihydroxyphenyl adamantane (7)
    Figure imgb0019
  • 3,8-dihydroxy-5a, 10b-diphenyl-coumarano-2 ', 3', 2,3-coumaran. (8th)

Die Erfindung schließt somit auch solche Gruppen R" ein, die mit den an die freien Valenzen gebundenen Phenylgruppen mehrfach verbrückt sind.The invention thus also includes those groups R "which are bridged several times with the phenyl groups bonded to the free valences.

Die Erfindung wird durch die nachfolgenden Beispiele näher erläutert.The invention is illustrated by the following examples.

Beispiel 1example 1

In einem 250 ml Rundkolben mit Rührer, Innenthermometer, Liebig-Kühler mit Vorlage. Tropftrichter und Argonzuleitung wurden 10,10 g (0,05 Mol) 4,4'-Dihydroxydiphenyläther, 17,36 g (0,05 Mol) 4,4'-Dichlortriphenylphosphinoxid (Reinheit > 98%), 7,30 (0,0525 Mol) Kaliumcarbonat, 75 ml N-methylpyrrolidon und 50 g Chlorbenzol zusammengegeben. Man erhitzte unter Inertgas auf Siedetemperatur und destillierte ein Wasser/Chlorbenzol-Gemisch ab. Als praktisch kein Chlorbenzol mehr überging, wurden langsam weitere 50 g Chlorbenzol zur Reaktionsmischung getropft und dieses gleichzeitig zusammen mit Resten des noch vorhandenen Wassers abdestilliert. Unter Erhöhen der Sumpftemperatur auf ca. 180°C wurde das Chlorbenzol soweit wie möglich entfernt.In a 250 ml round bottom flask with stirrer, internal thermometer, Liebig cooler with template. Dropping funnel and argon feed were 10.10 g (0.05 mol) of 4,4'-dihydroxydiphenyl ether, 17.36 g (0.05 mol) of 4,4'-dichlorotriphenylphosphine oxide (purity> 98%), 7.30 (0, 0525 mol) of potassium carbonate, 75 ml of N-methylpyrrolidone and 50 g of chlorobenzene combined. The mixture was heated to boiling temperature under inert gas and a water / chlorobenzene mixture was distilled off. When practically no chlorobenzene passed over, a further 50 g of chlorobenzene were slowly added dropwise to the reaction mixture, which was distilled off at the same time as residues of the water still present. The chlorobenzene was removed as far as possible while increasing the bottom temperature to approx. 180 ° C.

Die Reaktionsmischung wurde nun bei 180°C 44 Stunden erhitzt und anschließend bei dieser Temperatur 30 Minuten Chlormethan durchgeblasen. Nach dem Abkühlen wurde mit ca. 20 ml N-Methylpyrrolidon verdünnt und vom Ungelösten abfiltriert. Anschließend tropfte man die Mischung in 2 I Wasser/Methanol (v : v = 7: 3), sammelte das ausgefallene Polykondensat auf einem Filter, wusch mit 50 ml Methanol und trocknete das Produkt 20 Stunden lang bei Raumtemperatur im Luftstrom. Anschließend wurde der Polyäther in möglichst wenig Methylenchlorid gelöst und in Methanol ausgefällt. Das flockige, ausgefallene Produkt wurde abfiltriert und bei 80°C im Vakuum bis zur Gewichtskonstanz getrocknet (Ausbeute: 19,8 g).The reaction mixture was then heated at 180 ° C. for 44 hours and then chloromethane was blown through at this temperature for 30 minutes. After cooling, the mixture was diluted with about 20 ml of N-methylpyrrolidone and the undissolved solution was filtered off. The mixture was then added dropwise to 2 l of water / methanol (v: v = 7: 3), the precipitated polycondensate was collected on a filter, washed with 50 ml of methanol and the product was dried in an air stream at room temperature for 20 hours. The polyether was then dissolved in as little methylene chloride as possible and precipitated in methanol. The flaky, precipitated product was filtered off and dried at 80 ° C. in vacuo to constant weight (yield: 19.8 g).

Aus Chloroform erhält man eine klare, gelbe flexible Gießfolie (Mw nach GPC in DMF, Polystyrol als Eichsubstanz: 83 900).A clear, yellow, flexible cast film (Mw according to GPC in DMF, polystyrene as calibration substance: 83 900) is obtained from chloroform.

In einem Vergleichsversuch wurde die Reaktion bereits nach 10 Stunden abgebrochen. Man gewann aus Chlororform nur eine sehr spröde Gießfolie.In a comparative experiment, the reaction was stopped after only 10 hours. Only a very brittle cast film was obtained from Chlororform.

Beispiele 2 und 3Examples 2 and 3

Man setzte 0,05 Mol 4,4'-Dichlortriphenylphosphinoxid analog Beispiel 1 mit verschiedenen Bisphenolen um. Die variierten Parameter und die Ergebnisse sind in folgender Tabelle angegeben:

Figure imgb0020
0.05 mol of 4,4'-dichlorotriphenylphosphine oxide was reacted analogously to Example 1 with various bisphenols. The varied parameters and the results are given in the following table:
Figure imgb0020

Beispiel 4Example 4

Das Verfahren von Beispiel 1 wird auf die Umsetzung von 0,05 Mol 4,4'-Dichlordiphenylmethylphosphinoxid angewendet. Man erthält 16 g eines Polyethers mit einer spezifischen Viskosität von 0,50 dl/g,lin Chloroform).The procedure of Example 1 is applied to the reaction of 0.05 mole 4,4'-dichlorodiphenylmethylphosphine oxide. 16 g of a polyether with a specific viscosity of 0.50 dl / g, lin chloroform) are obtained.

Beispiel 5-9Example 5-9

Das Verfahren von Beispiel 1 wird auf die Umsetzung von 0,05 Mol 4,4'-Dichlortriphenylphosphinoxid angewendet.The procedure of Example 1 is applied to the reaction of 0.05 mole 4,4'-dichlorotriphenylphosphine oxide.

Die Ergebnisse sind in der folgenden Tabelle 11 zusammengefaßt.

Figure imgb0021
The results are summarized in Table 11 below.
Figure imgb0021

Claims (14)

1. Process for the preparation of phosphorus-containing polyarylene ethers of the structure
Figure imgb0029
having a reduced viscosity ηsp/c > 0.25 dl/g by polycondensation of a bis(chlorophenyl)phosphine oxide I with a bisphenol II at temperatures of 100 - 300 degreas C in the presence of a solvent for the polyarylene ether and in the presence of an amount of alkali equivalent to the amount of halogen
Figure imgb0030
Figure imgb0031
wherein
R is in each case a hydrogen atom, or R...R together are a covalent single bond or an oxygen atom, a sulphur atom or a sulphonyl, carbonyl, methylene or isopropylidene group,
R' is an alkyl or alkyl group,
R" is a single bond or an oxygen atom or a sulphur atom or an organic radical containing 5 to 15 C atoms, the free valencies of which start from quaternary C atoms, or the abovementioned formula II represents phenolphthalein,
E is an end group consisting of chlorine or hydrogen, or a hydroxyl or an alkyl or alkoxy, or aryl or aryloxy, or acyl or acyloxy group and
n is an average value of at least 10,
characterized in that the polycondensation is carried out in reaction times of at least 12 hours.
2. Process for the preparation of phosphorus-containing polyarylene ethers according to claim 1, characterized in that the polycondensation is carried out in reaction times of 12 to 80 hours.
3. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 and 2, characterized in that the polycondensation is carried out with I, in which R' is a methyl or phenyl group.
4. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 to 3, characterized in that the polycondensation is carried out with I, in which R is in each case a hydrogen atom.
5. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 to 3, characterized in that the polycondensation is carried out with I, in which R...R symbolizes a covalent single bond or an oxygen atom.
6. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 to 5, characterized in that the polycondensation is carried out with 11, in which R" is an oxygen atom.
7. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 to 5, characterized in that the polycondensation is carried out with 11, in which R" represents a single bond.
8. Process for the preparation of phosphorus -containing polyarylene ethers according to claims 1 to 5, characterized in that the polycondensation is carried out with 9,9-bis(4-hydroxyphenyl)fluorene as II.
9. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 to 5, characterized in that the polycondensation is carried out with phenolphthalein as II.
10. Process for the preparation of phosphorus-containing polyarylene ethers according to claims 1 to 5, characterized in that the polycondensation is carried out with 9,9-bis-4(hydroxyphenyl)xanthene.
11. Phosphorus-containing polyarylene ethers consisting of recurring units of the structure
Figure imgb0032
 wherein X is one of the groups
Figure imgb0033
having a reduced viscosity ηsp/c ≥ 0.25 dl/g.
12. Phosphorus-containing polyarylene ethers according to claim 11, 13 and 14, characterized by end groups F, Cl, OH or OCH3.
13. Phosphorus-containing polyarylene ethers consisting of recurring units of the structure
Figure imgb0034
14. Phosphorus-containing polyarylene ethers consisting of recurring units of the structure
Figure imgb0035
EP86107728A 1985-06-13 1986-06-06 Process for the preparation of polyarylene polyethers containing phosphorous Expired - Lifetime EP0205124B1 (en)

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DE3725058A1 (en) * 1987-07-29 1989-02-09 Roehm Gmbh THERMOPLASTICALLY PROCESSABLE POLYARYLENETHER WITH 9,9-BIS (4'-HYDROXYPHENYL) FLUORINE
DE3804988A1 (en) * 1988-02-18 1989-08-31 Roehm Gmbh HIGH-TEMPERATURE-RESISTANT AROMATIC POLYETHERS
JPH0326723A (en) * 1989-06-26 1991-02-05 Sumitomo Chem Co Ltd Preparation of aromatic polyether polymer
US5079333A (en) * 1990-07-13 1992-01-07 Virginia Tech Intellectual Properties, Inc. Novel mine-terminated poly(arylene ether phosphine oxide) oligomer
WO2012085985A1 (en) * 2010-12-24 2012-06-28 パナソニック株式会社 Polymer compound and method for producing same
CN103554478B (en) * 2013-10-13 2015-11-04 吉林大学 A kind of can the phosphorous polyaryletherketone of interlayer toughened bismaleimide resin based composites and toughened film thereof
CN109294203B (en) * 2018-10-10 2021-04-09 湖南七纬科技有限公司 Flame-retardant fireproof material for new energy automobile power battery and preparation method thereof
CN109867795A (en) * 2019-03-15 2019-06-11 上海应用技术大学 A kind of sulfonated polyether phosphine oxide polymer and its membrane preparation method containing phenolphthalein

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US4175175A (en) * 1963-07-16 1979-11-20 Union Carbide Corporation Polyarylene polyethers
US3784504A (en) * 1971-07-19 1974-01-08 Ici Ltd Thermoset resins prepared from dihydric phenol,dihalobenzenoid compound and polyhaloheterocyclic compound
DE2305413C2 (en) * 1973-02-03 1982-05-13 Bayer Ag, 5090 Leverkusen Branched aromatic polyaryl ether sulfones
DE3203186A1 (en) * 1982-01-30 1983-08-11 Röhm GmbH, 6100 Darmstadt POLYARYLENE ETHERS CONTAINING PHOSPHORUS
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